Quantum dot, curable composition comprising the same, cured layer using the composition, color filter including the cured layer, and display device including the cured layer

ABSTRACT

A quantum dot surface-modified with a specific compound, a non-solvent curable composition including the quantum dot, a solvent based curable composition including the quantum dot, a cured layer manufactured utilizing the curable composition, a color filter including the cured layer, and a display device including the cured layer are disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2019-0091233, filed in the Korean IntellectualProperty Office on Jul. 26, 2019, the entire content of which isincorporated herein by reference.

BACKGROUND 1. Field

This disclosure relates to a quantum dot, a curable compositionincluding the same, a cured layer utilizing the composition, a colorfilter including the cured layer, and a display device including thecured layer.

2. Description of the Related Art

In the case of general (e.g., related art) quantum dots, due tohydrophobic surface characteristics, a solvent in which the quantum dotscan be dispersed is limited. Thus, it is difficult to introduce (e.g.,add) the quantum dots into a polar system such as a binder or a curablemonomer.

For example, even in the case of a quantum dot ink composition (which isbeing actively researched), a polarity thereof is relatively low in aninitial step and it may be dispersed in a solvent utilized in thecurable composition having a high hydrophobicity. Because it isdifficult to increase quantum dots to be 20 wt % or more based on atotal amount of the composition, it is therefore difficult (e.g.,impossible) to increase light efficiency (e.g., luminous efficiency,quantum efficiency, etc.) of the ink over a certain level. Even thoughquantum dots are additionally added and dispersed in order to increaselight efficiency, a viscosity exceeds a range (e.g., 12 cPs) capable ofink-jetting and processability may be unsatisfactory. That is, when theviscosity of the quantum dot ink composition exceeds the range suitable(e.g., 12 cPs) for ink-jet printing due to the addition of additionalquantum dots, processability may be compromised.

In order to achieve the viscosity range capable of (e.g., suitable for)ink-jetting, a method of lowering an ink solid content by dissolving(e.g., adding) 50 wt % or more of a solvent based on a total amount ofthe composition has been utilized, which also provides a somewhatsatisfactory result in terms of viscosity. However, it may be consideredto be a satisfactory result in terms of viscosity, but nozzle drying(due to solvent volatilization (e.g., evaporation)), nozzle clogging,loss of a layer (e.g., reduction of a layer width or thickness) as timepassed after jetting may become worse and it is difficult to control athickness deviation after curing. Thus, it is difficult to apply it(e.g., this method) to actual processes.

Therefore, a non-solvent based quantum dot ink that does not include asolvent is the embodied (e.g., most preferable) form to be applied to anactual process. The current technique of applying a quantum dot itselfto a solvent based composition is now limited to a certain extent.

Currently, the embodied (e.g., most preferred) solvent based compositionto be applied to actual processes is that the quantum dots, which arenot surface-modified, such as ligand-substitution, are included in acontent of about 20 wt % to 25 wt % based on a total amount of thesolvent based composition. Therefore, it is difficult to increase lightefficiency and absorption rate due to the viscosity limitation.Meanwhile, attempts have been made to lower the quantum dot content andincrease the content of the light diffusing agent (scatterer) in otherimprovement directions, but this has also failed to solve asedimentation problem and a low light efficiency problem.

SUMMARY

An aspect according to embodiments of the present disclosure is directedtoward providing a surface-modified quantum dot having improved opticalcharacteristics.

Another aspect according to embodiments of the present disclosure isdirected toward providing a non-solvent curable composition includingthe quantum dot.

Another aspect according to embodiments of the present disclosure isdirected toward providing a solvent based curable composition includingthe quantum dot.

Another aspect according to embodiments of the present disclosure isdirected toward providing a cured layer manufactured utilizing thecomposition.

Another aspect according to embodiments of the present disclosure isdirected toward providing a color filter including the cured layer.

Another aspect according to embodiments of the present disclosure isdirected toward providing a display device including the cured layerand/or the color filter.

According to an embodiment, a quantum dot is surface-modified with acompound represented by Chemical Formula 1.

In Chemical Formula 1,

R¹ is a substituted or unsubstituted C1 to C10 alkyl group or asubstituted or unsubstituted C6 to C20 aryl group,

L¹ to L³ are each independently a substituted or unsubstituted C1 to C10alkylene group, an ester group, or an ether group,

n is an integer of 3 to 20, provided that when L² is an ester group andL³ is an unsubstituted C1 to C10 alkylene group, n is an integer of 4 to20.

L¹ and L³ may each independently be a substituted or unsubstituted C1 toC10 alkylene group and L² may be an ester group or an ether group.

The compound represented by Chemical Formula 1 may include at least oneselected from compounds represented by Chemical Formula 1-1 to ChemicalFormula 1-9.

The quantum dot may have a maximum fluorescence emission wavelength atabout 500 nm to about 680 nm.

According to another embodiment, a non-solvent curable compositionincludes the quantum dot surface-modified with the compound representedby Chemical Formula 1; a polymerizable monomer having a carbon-carbondouble bond at a terminal end; and a light diffusing agent, wherein thepolymerizable monomer is about 35 wt % to about 80 wt % in amount basedon a total weight of the non-solvent curable composition.

The polymerizable monomer may have a molecular weight of about 220 g/molto about 1,000 g/mol.

The polymerizable monomer may be represented by Chemical Formula 2.

In Chemical Formula 2,

R² and R³ are each independently a hydrogen atom or a substituted orunsubstituted C1 to C10 alkyl group,

L⁴ and L⁶ are each independently a substituted or unsubstituted C1 toC10 alkylene group, and

L⁵ is a substituted or unsubstituted C1 to C10 alkylene group or ethergroup.

The quantum dot may be about 1 wt % to about 60 wt % in amount based ona total weight of the non-solvent curable composition.

The light diffusing agent may include barium sulfate, calcium carbonate,titanium dioxide, zirconia, or a combination thereof.

The non-solvent curable composition may further include a polymerizationinitiator.

The non-solvent curable composition may further include a polymerizationinhibitor; malonic acid; 3-amino-1,2-propanediol; a silane-basedcoupling agent; a leveling agent; a fluorine-based surfactant; or acombination thereof.

According to another embodiment, a solvent based curable compositionincludes the compound represented by Chemical Formula 1 that issurface-modified quantum dot; a binder resin; and a solvent.

The solvent based curable composition may further include apolymerizable monomer, a polymerization initiator, a light diffusingagent, or a combination thereof.

The solvent based curable composition may be a photosensitive resincomposition.

According to another embodiment, a cured layer manufactured utilizingthe composition is provided.

According to another embodiment, a color filter including the curedlayer is provided.

In addition, according to another embodiment, a display device includingthe color filter is provided.

Other embodiments of the present disclosure are included in thefollowing detailed description.

According to embodiments of the present disclosure, a quantum dot issurface-modified with a specific ligand. The surface-modified quantumdot may be more easily applied to all of photocurable compositions,solvent based thermosetting compositions, and non-solvent thermosettingcompositions as compared to related art quantum dots, and thus may haveimproved viscosity and optical characteristics as well asprocessability.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present disclosure are described in moredetail. However, these embodiments are exemplary, the present disclosureis not limited thereto and the subject matter of the present disclosureis defined by the scope of claims and equivalents thereof.

As used herein, when specific definition is not otherwise provided, theterm “alkyl group” refers to a C1 to C20 alkyl group, the term “alkenylgroup” refers to a C2 to C20 alkenyl group, the term “cycloalkenylgroup” refers to a C3 to C20 cycloalkenyl group, the term“heterocycloalkenyl group” refers to a C2 to C20 heterocycloalkenylgroup, the term “aryl group” refers to a C6 to C20 aryl group, the term“arylalkyl group” refers to a C6 to C20 arylalkyl group, the term“alkylene group” refers to a C1 to C20 alkylene group, the term “arylenegroup” refers to a C6 to C20 arylene group, the term “alkylarylenegroup” refers to a C6 to C20 alkylarylene group, the term “heteroarylenegroup” refers to a C3 to C20 heteroarylene group, and the term“alkoxylene group” refers to a C1 to C20 alkoxylene group.

As used herein, when specific definition is not otherwise provided, theterm “substituted” refers to replacement of at least one hydrogen atomby a substituent selected from a halogen atom (F, Cl, Br, or I), ahydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group,an amine group, an imino group, an azido group, an amidino group, ahydrazino group, a hydrazono group, a carbonyl group, a carbamyl group,a thiol group, an ester group, an ether group, a carboxyl group or asalt thereof, a sulfonic acid group or a salt thereof, a phosphoric acidor a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, aC2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkylgroup, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, aC2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group,a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, anda combination thereof.

As used herein, when specific definition is not otherwise provided, theterm “hetero” refers to inclusion of at least one heteroatom selectedfrom N, O, S, and P, in addition to carbon atom(s), in the chemicalformula.

As used herein, when specific definition is not otherwise provided, theterm “(meth)acrylate” refers to both “acrylate” and “methacrylate”, andthe term “(meth)acrylic acid” refers to both “acrylic acid” and“methacrylic acid.”

As used herein, when specific definition is not otherwise provided, theterm “combination” refers to mixing or copolymerization.

As used herein, when a definition is not otherwise provided, hydrogen isbonded at the position where a chemical bond is supposed to exist butnot drawn in a chemical formula.

As used herein, a cardo-based resin refers to a resin including at leastone functional group represented by one selected from Chemical Formula3-1 to Chemical Formula 3-11 in the backbone of the resin.

In addition, in the present specification, when a definition is nototherwise provided, “*” refers to a linking point with the same ordifferent atom or chemical formula.

A quantum dot according to an embodiment may be a quantum dot that issurface-modified with a ligand having a polar group, i.e., a ligandhaving high affinity to a polymerizable monomer having a carbon-carbondouble bond at the terminal end. In the case of the above-describedsurface-modified quantum dots, it is easy (e.g., very easy) to producehigh-concentration or highly-concentrated quantum dot dispersion (withimprovement of dispersibility of quantum dots for monomers), therebyrealizing a non-solvent curable composition and significantly (e.g.,greatly) improving light efficiency.

For example, the ligand having the polar group may have a structurehaving a high affinity to a chemical structure of the monomer includingthe compound having the carbon-carbon double bond.

For example, the ligand having the polar group may be represented byChemical Formula 1, but the present disclosure is not necessarilylimited thereto.

In Chemical Formula 1,

R¹ is a substituted or unsubstituted C1 to C10 alkyl group or asubstituted or unsubstituted C6 to C20 aryl group,

L¹ to L³ are each independently a substituted or unsubstituted C1 to C10alkylene group, an ester group, or an ether group, and

n is an integer of 3 to 20, provided that when L² is an ester group andL³ is an unsubstituted C1 to C10 alkylene group, n is an integer of 4 to20.

For example, in Chemical Formula 1, L¹ and L³ may each independently bea substituted or unsubstituted C1 to C10 alkylene group, and L² may bean ester group (*—C(═O)O—* or *—O(C═O)—*) or an ether group (*—O—*).

The compound represented by Chemical Formula 1 may include at least oneselected from compounds represented by Chemical Formula 1-1 to ChemicalFormula 1-9, but the present disclosure is not necessarily limitedthereto.

In case that the compound represented by Chemical Formula 1, forexample, the compound represented by one of Chemical Formula 1-1 toChemical Formula 1-9, is utilized as a ligand, it is easier tosurface-modify the quantum dot. When the quantum dot surface-modifiedwith the ligand is added to the aforementioned monomers and is stirred,a transparent (e.g., very transparent) dispersion may be obtained, whichis a measure to confirm that the quantum dot is well surface-modified.

For example, the quantum dot may have a maximum fluorescence emissionwavelength of about 500 nm to about 680 nm.

A non-solvent curable composition according to another embodimentincludes the quantum dot according to an embodiment (the quantum dotsurface-modified with the compound of Chemical Formula 1), apolymerizable monomer, and a light diffusing agent, wherein thepolymerizable monomer is included in an amount of about 35 wt % to about80 wt % based on a total amount of the non-solvent curable composition.

An embodiment relates to a non-solvent curable composition including aquantum dot. In one embodiment, the quantum dot-containing curablecomposition (ink) has been developed to include (e.g., specificallyutilize) a thiol binder or monomer (a resin for a quantum dot sheet(film) including 4T (e.g., monomer with four thiol groups)) that hasgood compatibility with the quantum dot.

On the other hand, because a generally and widely utilized polymerizablemonomer, an -ene-based monomer (including a vinyl-based monomer, anacrylate-based monomer, a methacrylate-based monomer, and/or the likewhich include a mono-functional monomer or a multi-functional monomer)has low compatibility with the quantum dot and is limited in terms ofdispersibility of the quantum dot, various developments for usefullyapplying it to the curable composition including the quantum dot aresubstantially difficult. In addition, the -ene-based monomer does notshow high concentration quantum dot dispersibility and thus hasdifficulties in being applied to (e.g., included in) the curablecomposition including the quantum dot.

Because of this drawback, the curable composition including the quantumdot has been developed to have a composition including a solvent in aconsiderable amount (greater than or equal to about 50 wt %). But whenthe solvent content is increased, ink-jetting processability may bedeteriorated. Accordingly, in order to satisfy the ink-jettingprocessability, a demand for a non-solvent curable composition iscontinuously increased.

An embodiment of the present disclosure relates to the increasing demandfor the non-solvent curable composition, which may have an effect (e.g.,a passivation effect) of not deteriorating inherent opticalcharacteristics of the quantum dot as well as providing highconcentration dispersibility of the quantum dots even in a solvent-freesystem (by including about 40 wt % to about 80 wt % of the polymerizablemonomer including a compound having a carbon-carbon double bond at theterminal end along with the quantum dot based on a total weight of thecurable composition) and thus improving affinity of the quantum dots tothe curable composition.

Hereinafter, each component is specifically described in more detail.

Quantum Dot

The quantum dot included in the non-solvent curable composition may be aquantum dot surface-modified with the compound represented by ChemicalFormula 1, but the present disclosure is not necessarily limitedthereto.

For example, the quantum dot absorbs light in a wavelength region ofabout 360 nm to about 780 nm, for example, about 400 nm to about 780 nm,and emits fluorescence in a wavelength region of about 500 nm to about700 nm, for example about 500 nm to about 580 nm, or about 600 nm toabout 680 nm. That is, the quantum dot may have a maximum fluorescenceemission wavelength (λ_(em)) at about 500 nm to about 680 nm.

The quantum dots may each independently have a full width at halfmaximum (FWHM) of about 20 nm to about 100 nm, for example, about 20 nmto about 50 nm. When the quantum dot has a full width at half maximum(FWHM) of these ranges, color reproducibility is increased when utilizedas a color material in a color filter due to high color purity.

The quantum dots may each independently be an organic material, aninorganic material, or a hybrid (mixture) of an organic material and aninorganic material.

The quantum dots may each independently include (e.g., be composed of) acore and a shell around (e.g., surrounding) the core, and the core andthe shell may each independently have a structure of a core, core/shell,core/first shell/second shell, alloy, alloy/shell, and/or the like, eachcomposed of Group II-IV elements, Group III-V elements, and/or the like,but the present disclosure is not limited thereto.

For example, the core may include at least one material selected fromCdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP,InAs, and an alloy thereof, but the present disclosure is notnecessarily limited thereto. The shell around (e.g., surrounding) thecore may include at least one material selected from CdSe, ZnSe, ZnS,ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and an alloy thereof, but the presentdisclosure is not necessarily limited thereto.

In an embodiment, because an interest in the environment has recentlybeen much increased over the whole world, and a regulation of a toxicmaterial has also been fortified (e.g., tightened), a non-cadmium-basedlight emitting material (InP/ZnS, InP/ZnSe/ZnS, etc.) having slightlylower (e.g., little low) quantum efficiency (quantum yield) but beingenvironmentally-friendly (instead of a light emitting material having acadmium-based core) is utilized, but the present disclosure is notnecessarily limited thereto.

In the case of the quantum dots of the core/shell structure, an entiresize including the shell (an average particle diameter) may be about 1nm to about 15 nm, for example, about 5 nm to about 15 nm.

For example, the quantum dots may each independently be a red quantumdot, a green quantum dot, or a combination thereof. The red quantum dotsmay each independently have an average particle diameter of about 10 nmto about 15 nm. The green quantum dots may each independently have anaverage particle diameter of about 5 nm to about 8 nm.

Also, for dispersion stability of the quantum dots, the non-solventcurable composition according to an embodiment may further include adispersing agent. The dispersing agent helps with the uniformdispersibility of a photo-conversion material such as a quantum dot inthe non-solvent curable composition and may include a non-ionic,anionic, and/or cationic dispersing agent. For example, the dispersingagent may be polyalkylene glycol or esters thereof, a polyoxy alkylene,a polyhydric alcohol ester alkylene oxide addition product, an alcoholalkylene oxide addition product, a sulfonate ester, a sulfonate salt, acarboxylate ester, a carboxylate salt, an alkyl amide alkylene oxideaddition product, an alkyl amine and/or the like, and may be utilizedalone or in a mixture of two or more. The dispersing agent may beutilized in an amount of about 0.1 wt % to about 100 wt %, for example,about 10 wt % to about 20 wt %, relative to a solid content of thephoto-conversion material such as quantum dots.

The quantum dots, for example, the surface-modified quantum dots may beincluded in an amount of about 1 wt % to about 60 wt %, for example,about 5 wt % to about 50 wt %, based on a total solid amount of thenon-solvent curable composition. When the quantum dots, for example, thesurface-modified quantum dots, are included within these ranges, aphoto-conversion rate may be improved, and pattern characteristics anddevelopment characteristics may not be interfered with, so that thenon-solvent curable composition may have suitable (e.g., excellent)processability.

Polymerizable Monomer Having Carbon-Carbon Double Bond at the TerminalEnd

The monomer having the carbon-carbon double bond at the terminal end may(e.g., should) be included in an amount of about 35 wt % to about 80 wt% based on a total amount of the non-solvent curable composition. Forexample, the monomer having the carbon-carbon double bond at theterminal end may be included in an amount of about 40 wt % to about 80wt % based on a total amount of the non-solvent curable composition.When the monomer having the carbon-carbon double bond at the terminalend is included within these ranges, a non-solvent curable compositionhaving a viscosity capable of (e.g., suitable for) ink-jetting may beprepared and the quantum dots in the prepared non-solvent curablecomposition may have improved dispersibility, thereby improving opticalcharacteristics.

For example, the monomer having the carbon-carbon double bond at theterminal end may have a molecular weight of about 220 g/mol to about1,000 g/mol. When the monomer having the carbon-carbon double bond atthe terminal end has a molecular weight within this range, it may besuitable (e.g., advantageous) for ink-jetting because it does notincrease the viscosity of the composition and does not hinder theoptical characteristics of the quantum dot.

For example, the monomer having the carbon-carbon double bond at theterminal end may be represented by Chemical Formula 2, but the presentdisclosure is not necessarily limited thereto.

In Chemical Formula 2,

R² and R³ are each independently a hydrogen atom or a substituted orunsubstituted C1 to C10 alkyl group,

L⁴ and L⁶ are each independently a substituted or unsubstituted C1 toC10 alkylene group, and

L⁵ is a substituted or unsubstituted C1 to C10 alkylene group or anether group.

For example, the monomer having the carbon-carbon double bond at theterminal end may be represented by Chemical Formula 2-1 or 2-2, but thepresent disclosure is not necessarily limited thereto.

For example, the monomer having the carbon-carbon double bond at theterminal end may further include ethylene glycoldiacrylate, triethyleneglycoldiacrylate, 1,4-butanedioldiacrylate, 1,6-hexanedioldiacrylate,neopentylglycoldiacrylate, pentaerythritoldiacrylate,pentaerythritoltriacrylate, dipentaerythritoldiacrylate,dipentaerythritoltriacrylate, dipentaerythritolpentaacrylate,pentaerythritolhexaacrylate, bisphenol A diacrylate,trimethylolpropanetriacrylate, novolacepoxyacrylate, ethyleneglycoldimethacrylate, triethylene glycoldimethacrylate, propyleneglycoldimethacrylate, 1,4-butanedioldimethacrylate,1,6-hexanedioldimethacrylate, or a combination thereof in addition tothe aforementioned compound of Chemical Formula 2-1 or Chemical Formula2-2.

In addition, together with the monomer having the carbon-carbon doublebond at the terminal end, a suitable (e.g., generally-utilized) monomerof a related art thermosetting or photocurable composition may befurther included. For example the monomer may further include anoxetane-based compound such as bis[1-ethyl (3-oxetanyl)]methyl ether,and/or the like.

Light Diffusing Agent (or Light Diffusing Agent Dispersion)

The non-solvent curable composition according to an embodiment mayinclude a light diffusing agent.

For example, the light diffusing agent may include barium sulfate(BaSO₄), calcium carbonate (CaCO₃), titanium dioxide (TiO₂), zirconia(ZrO₂), or a combination thereof.

The light diffusing agent may reflect unabsorbed light in theaforementioned quantum dots and allow the quantum dots to absorb thereflected light again. That is, the light diffusing agent may increasean amount of light absorbed by the quantum dots and increasephoto-conversion efficiency of the curable composition.

The light diffusing agent may have an average particle diameter (D₅₀) ofabout 100 nm to about 250 nm and for example, about 150 nm to about 230nm. When the average particle diameter of the light diffusing agent iswithin these ranges, it may have a better light diffusing effect andincrease photo-conversion efficiency.

The light diffusing agent may be included in an amount of about 1 wt %to about 20 wt %, for example about 5 wt % to about 10 wt % based on atotal solid amount of the non-solvent curable composition. When thelight diffusing agent is included in an amount of less than about 1 wt %based on a total amount of the non-solvent curable composition, it isdifficult to expect a photo-conversion efficiency improvement effect dueto the usage of the light diffusing agent, while when it is included inan amount of greater than about 20 wt %, there is a possibility that thequantum dot may be precipitated.

Polymerization Initiator

The photopolymerization initiator is a suitable (e.g.,generally-utilized) initiator for a photosensitive resin composition,for example, an acetophenone-based compound, a benzophenone-basedcompound, a thioxanthone-based compound, a benzoin-based compound, atriazine-based compound, an oxime-based compound, an aminoketone-basedcompound, and/or the like, but the present disclosure is not necessarilylimited thereto.

Examples of the acetophenone-based compound may be 2,2′-diethoxyacetophenone, 2,2′-dibutoxy acetophenone,2-hydroxy-2-methylpropinophenone, p-t-butyltrichloro acetophenone,p-t-butyldichloro acetophenone, 4-chloro acetophenone,2,2′-dichloro-4-phenoxy acetophenone,2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and/or thelike.

Examples of the benzophenone-based compound may be benzophenone, benzoylbenzoate, benzoyl methyl benzoate, 4-phenyl benzophenone,hydroxybenzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-dimethylaminobenzophenone, 4,4′-dichlorobenzophenone,3,3′-dimethyl-2-methoxybenzophenone, and/or the like.

Examples of the thioxanthone-based compound may be thioxanthone,2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone,2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, and/or the like.

Examples of the benzoin-based compound may be benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylether, benzyldimethylketal, and/or the like.

Examples of the triazine-based compound may be2,4,6-trichloro-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-(3′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(4′-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine,2-biphenyl-4,6-bis(trichloro methyl)-s-triazine,bis(trichloromethyl)-6-styryl-s-triazine,2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2,4-bis(trichloromethyl)-6-piperonyl-s-triazine,2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and/or thelike.

Examples of the oxime-based compound may be O-acyloxime-based compound,2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octandione,1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and/or the like.Non-limiting specific examples of the O-acyloxime-based compound may be1,2-octandione,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one,1-(4-phenylsulfanyl phenyl)-butane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octane-1,2-dione-2-oxime-O-benzoate,1-(4-phenylsulfanyl phenyl)-octan-1-oneoxime-O-acetate,1-(4-phenylsulfanyl phenyl)-butan-1-oneoxime-O-acetate, and/or the like.

Examples of the am inoketone-based compound may be2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and/or thelike.

The photopolymerization initiator may further include a carbazole-basedcompound, a diketone-based compound, a sulfonium borate-based compound,a diazo-based compound, an imidazole-based compound, a biimidazole-basedcompound, and/or the like, besides the compounds described above.

The photopolymerization initiator may be utilized with a photosensitizercapable of causing a chemical reaction by absorbing light and becomingexcited and then, transferring its energy.

Examples of the photosensitizer may be tetraethylene glycolbis-3-mercapto propionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercapto propionate, and/or thelike.

Examples of the thermal polymerization initiator may be peroxide, suchas benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilaurylperoxide, di-tert-butyl peroxide, cyclohexane peroxide, methyl ethylketone peroxide, hydroperoxide (e.g., tert-butyl hydroperoxide, cumenehydroperoxide), dicyclohexyl peroxydicarbonate, t-butyl peroxybenzoate,and/or the like; azo polymerization initiators, such as2,2-azo-bis(isobutyronitrile), 2,2′-azobis-2-methylpropinonitrile,and/or the like, but the present disclosure is not necessarily limitedthereto and any suitable thermal polymerization initiator (e.g., ofwhich is well known in the art) may be utilized.

The polymerization initiator may be included in an amount of about 0.1wt % to about 5 wt %, for example, about 1 wt % to about 4 wt %, basedon a total amount of a non-solvent curable composition. When thepolymerization initiator is included in these ranges, it is possible toobtain suitable (e.g., excellent) reliability due to sufficient curing(during exposure or thermal curing) and to reduce or preventdeterioration of transmittance (due to non-reaction initiators), therebyreducing or preventing deterioration of optical characteristics of thequantum dots.

Other Additives

For stability and dispersion improvement of the quantum dots, thenon-solvent curable composition according to an embodiment may furtherinclude a polymerization inhibitor.

The polymerization inhibitor may include a hydroquinone-based compound,a catechol-based compound, or a combination thereof, but the presentdisclosure is not necessarily limited thereto. When the non-solventcurable composition according to an embodiment further includes thehydroquinone-based compound, the catechol-based compound, or thecombination thereof, room temperature cross-linking during exposureafter coating the non-solvent curable composition may be prevented orinhibited.

For example, the hydroquinone-based compound, the catechol-basedcompound, or the combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone,2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butylcatechol, 4-methoxyphenol, pyrogallol, 2,6-di-t-butyl-4-methylphenol,2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O′)aluminum, or acombination thereof, but the present disclosure is not necessarilylimited thereto.

The hydroquinone-based compound, the catechol-based compound, or thecombination thereof may be utilized in a form of dispersion. Thepolymerization inhibitor in a form of dispersion may be included in anamount of about 0.001 wt % to about 3 wt %, for example, about 0.1 wt %to about 2 wt %, based on a total amount of the non-solvent curablecomposition. When the polymerization inhibitor is included in theseranges, passage of time at room temperature may be solved andsimultaneously sensitivity deterioration and surface delaminationphenomenon may be reduced or prevented. That is, when the polymerizationinhibitor is included in these ranges, the room temperature stability ofthe non-solvent curable composition may be improved, and reduction incuring sensitivity and delamination of the coating layer may both bereduced or prevented.

In addition, the non-solvent curable composition according to anembodiment may further include malonic acid; 3-amino-1,2-propanediol; asilane-based coupling agent; a leveling agent; a fluorine-basedsurfactant; or a combination thereof in order to improve heat resistanceand reliability.

For example, the non-solvent curable composition according to anembodiment may further include a silane-based coupling agent having areactive substituent such as a vinyl group, a carboxyl group, amethacryloxy group, an isocyanate group, an epoxy group and/or the likein order to improve close contacting (e.g., adhesion) properties with asubstrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxy propyl trimethoxysilane,β-epoxycyclohexylethyltrimethoxysilane, and/or the like, and thesilane-based coupling agent may be utilized alone or in a mixture of twoor more.

The silane-based coupling agent may be utilized in an amount of about0.01 parts by weight to about 10 parts by weight based on 100 parts byweight of the non-solvent curable composition. When the silane-basedcoupling agent is included within this range, close contacting (e.g.,adhesion) properties, storage capability, and/or the like are suitable(e.g., excellent).

In addition, the non-solvent curable composition may further include asurfactant, for example, a fluorine-based surfactant, as needed in orderto improve coating properties and inhibit generation of spots, that is,to improve leveling performance.

The fluorine-based surfactant may have a low weight average molecularweight of about 4,000 g/mol to about 10,000 g/mol, and for example,about 6,000 g/mol to about 10,000 g/mol. In addition, the fluorine-basedsurfactant may have a surface tension of 18 mN/m to 23 mN/m (measured ina 0.1% polyethylene glycol monomethylether acetate (PGMEA) solution).When the fluorine-based surfactant has a weight average molecular weightand a surface tension within the ranges described above, levelingperformance may be further improved, and suitable (e.g., excellent)characteristics may be provided when slit coating as high speed coatingis applied because less film defects may be generated by reducing orpreventing a spot generation during the high speed coating andsuppressing a vapor generation. That is, when the fluorine-basedsurfactant has a weight average molecular weight and a surface tensionwithin the ranges described above, leveling performance may be furtherimproved, and when coated utilizing high speed slit coating, spotgeneration and vapor generation may be reduced or prevented, therebyreducing film defects.

Examples of the fluorine-based surfactant may be, BM-1000®, and BM-1100®(BM Chemie Inc.); MEGAFACE F 142D®, F 172®, F 173®, and F 183®(Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135®, FULORADFC-170C®, FULORAD FC-430®, and FULORAD FC-431° (Sumitomo 3M Co., Ltd.);SURFLON S-112®, SURFLON S-113®, SURFLON S-131®, SURFLON S-141®, andSURFLON S-145® (ASAHI Glass Co., Ltd.); and SH-28PA®, SH-190®, SH-193®,SZ-6032®, and SF-8428®, and the like (Toray Silicone Co., Ltd.); andF-482, F-484, F-478, F-554 and the like of DIC Co., Ltd.

In addition, the non-solvent curable composition according to anembodiment may include a silicone-based surfactant in addition to thefluorine-based surfactant. Specific examples of the silicone-basedsurfactant may be TSF400, TSF401, TSF410, TSF4440, and the like ofToshiba silicone Co., Ltd., but the present disclosure is not limitedthereto.

The surfactant may be included in an amount of about 0.01 parts byweight to about 5 parts by weight, for example, about 0.1 parts byweight to about 2 parts by weight, based on 100 parts by weight of thenon-solvent curable composition. When the surfactant is included withinthese ranges, less foreign materials are produced (or included) in asprayed composition.

In addition, the non-solvent curable composition according to anembodiment may further include other additives such as an antioxidant, astabilizer, and/or the like in a set or predetermined amount, unlessdesired properties are deteriorated (when these additives are included).

Another embodiment provides a solvent based curable compositionincluding the quantum dot surface-modified with the compound representedby Chemical Formula 1, a binder resin, and a solvent.

The quantum dot surface-modified with the compound represented byChemical Formula 1 is the same as described above. However, the quantumdot surface-modified with the compound represented by Chemical Formula 1may be included in an amount of about 1 wt % to about 40 wt %, forexample, about 1 wt % to about 30 wt %, based on a total amount of thesolvent based curable composition. When the quantum dot surface-modifiedwith the compound represented by Chemical Formula 1 is included withinthese ranges, a photo-conversion rate may be improved, and patterncharacteristics and development characteristics may not be interferedwith, so that the non-solvent curable composition may have suitable(e.g., excellent) processability.

Binder Resin

The binder resin may include an acryl-based resin, a cardo-based resin,an epoxy resin, or a combination thereof.

The acryl-based resin is a copolymer of a first ethylenic unsaturatedmonomer and a second ethylenic unsaturated monomer that arecopolymerizable with each other, and may be a resin including at leastone acryl-based repeating unit.

The first ethylenic unsaturated monomer is an ethylenic unsaturatedmonomer including at least one carboxyl group, and examples of themonomer include acrylic acid, methacrylic acid, maleic acid, itaconicacid, fumaric acid, and/or a combination thereof.

The first ethylenic unsaturated monomer may be included in an amount ofabout 5 wt % to about 50 wt %, for example, about 10 wt % to about 40 wt%, based on a total amount of the acryl-based binder resin.

The second ethylenic unsaturated monomer may be an aromatic vinylcompound (such as styrene, a-methylstyrene, vinyl toluene,vinylbenzylmethylether and/or the like); an unsaturated carboxylateester compound (such as methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate,phenyl(meth)acrylate, and/or the like); an unsaturated amino alkylcarboxylate ester compound (such as 2-aminoethyl(meth)acrylate,2-dimethylaminoethyl(meth)acrylate, and/or the like); a carboxylic acidvinyl ester compound (such as vinyl acetate, vinyl benzoate, and/or thelike); an unsaturated glycidyl carboxylate ester compound (such asglycidyl(meth)acrylate, and/or the like); a vinyl cyanide compound (suchas (meth)acrylonitrile and/or the like); an unsaturated amide compound(such as (meth)acrylamide, and/or the like); and/or the like, and may beutilized alone or as a mixture of two or more.

Specific examples of the acryl-based binder resin may be apolybenzylmethacrylate, (meth)acrylic acid/benzylmethacrylate copolymer,a (meth)acrylic acid/benzylmethacrylate/styrene copolymer, a(meth)acrylic acid/benzylmethacrylate/2-hydroxyethylmethacrylatecopolymer, a (meth)acrylicacid/benzylmethacrylate/styrene/2-hydroxyethylmethacrylate copolymer,and/or the like, but the present disclosure is not limited thereto, andthe acryl-based resin may be utilized alone or as a mixture of two ormore.

A weight average molecular weight of the acryl-based binder resin may beabout 5,000 g/mol to about 15,000 g/mol. When the acryl-based binderresin has a weight average molecular weight within this range, closecontacting (e.g., adhesion) properties to a substrate, physical andchemical properties are improved, and a viscosity of the solvent-basedcurable composition is appropriate (e.g., suitable).

The cardo-based resin may include a repeating unit represented byChemical Formula 3.

In Chemical Formula 3,

R³¹ and R³² are each independently a hydrogen atom or a substituted orunsubstituted (meth)acryloyloxy alkyl group,

R³³ and R³⁴ are each independently a hydrogen atom, a halogen atom, or asubstituted or unsubstituted C1 to C20 alkyl group,

Z¹ is a single bond, O, CO, SO₂, CR³⁵R³⁶, SiR³⁷R³⁸ (wherein, R³⁵ to R³⁸are each independently a hydrogen atom or a substituted or unsubstitutedC1 to C20 alkyl group), or one of linking groups represented by ChemicalFormula 3-1 to Chemical Formula 3-11.

In Chemical Formula 3-5,

R^(a) is a hydrogen atom, an ethyl group, C₂H₄Cl, C₂H₄OH, CH₂CH═CH₂, ora phenyl group.

Z² is an acid anhydride residual group, and

t1 and t2 are each independently an integer from 0 to 4.

A weight average molecular weight of the cardo-based binder resin may beabout 500 g/mol to about 50,000 g/mol, for example, about 1,000 g/mol toabout 30,000 g/mol. When the weight average molecular weight of thecardo-based binder resin is within these ranges, a satisfactory patternmay be formed without a residue during a manufacture of a cured layer(e.g., during the curing process of the coating layer) and withoutlosing a film thickness during development of the solvent based curablecomposition.

The cardo-based binder resin may include a functional group representedby Chemical Formula 4 at at least one terminal end of the two (i.e.,both) terminal ends.

In Chemical Formula 4,

Z³ is represented by one of Chemical Formula 4-1 to Chemical Formula4-7.

In Chemical Formula 4-1, R^(b) and R^(c) are each independently ahydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, anester group, or an ether group.

In Chemical Formula 4-5, R^(d) is O, S, NH, a substituted orunsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, ora C2 to C20 alkenylamine group.

The cardo-based resin may be, for example, prepared by mixing at leasttwo selected from a fluorene-containing compound (such as9,9-bis(4-oxiranylmethoxyphenyl)fluorene); an anhydride compound (suchas benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylicacid dianhydride, biphenyltetracarboxylic acid dianhydride,benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride,cyclobutanetetracarboxylic acid dianhydride, perylenetetracarboxylicacid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride,and/or tetrahydrophthalic anhydride); a glycol compound (such asethylene glycol, propylene glycol, and/or polyethylene glycol); analcohol compound (such as methanol, ethanol, propanol, n-butanol,cyclohexanol, and/or benzylalcohol); a solvent-based compound (such aspropylene glycol methylethylacetate, and/or N-methylpyrrolidone); aphosphorus compound (such as triphenylphosphine); and an amine orammonium salt compound (such as tetramethylammonium chloride,tetraethylammonium bromide, benzyldiethylamine, triethylamine,tributylamine, and/or benzyltriethylammonium chloride).

When the binder resin is a cardo-based resin, the solvent based curablecomposition including the binder resin, for example (e.g.,particularly), the photosensitive resin composition, may have suitable(e.g., excellent) developability and sensitivity during photo-curing andthus, may have suitable (e.g., fine) pattern-forming capability.

An acid value of the acryl-based resin may be about 80 mgKOH/g to about130 mgKOH/g. When the acryl-based resin has an acid value within thisrange, suitable (e.g., excellent) resolution of a pixel may be obtained.

The epoxy resin may be a thermally polymerizable monomer or oligomer,and may include a compound having a carbon-carbon unsaturated bond and acarbon-carbon cyclic bond.

The epoxy resin may further include a bisphenol A epoxy resin, abisphenol F epoxy resin, a phenol novolac epoxy resin, a cyclicaliphatic epoxy resin, and/or an aliphatic polyglycidyl ether, but thepresent disclosure is not necessarily limited thereto.

Suitable commercially available product of the compound (e.g., epoxyresin) may be a bisphenyl epoxy resin (such as YX4000, YX4000H, YL6121H,YL6640, or YL6677 of Yuka Shell Epoxy Co.); a cresol novolac epoxy resin(such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, andEOCN-1027 of Nippon Kayaku Co. Ltd. and EPIKOTE 180S75, and the like ofYuka Shell Epoxy Co.); a bisphenol A epoxy resin (such as EPIKOTE 1001,1002, 1003, 1004, 1007, 1009, 1010 and 828 of Yuka Shell Epoxy Co.); abisphenol F epoxy resin (such as EPIKOTE 807 and 834 of Yuka Shell EpoxyCo.); a phenol novolac epoxy resin (such as EPIKOTE 152, 154, or 157H65of Yuka Shell Epoxy Co. and EPPN 201, 202 of Nippon Kayaku Co. Ltd.); acyclic aliphatic epoxy resin (such as CY175, CY177 and CY179 ofCIBA-GEIGY A.G Corp., ERL-4234, ERL-4299, ERL-4221 and ERL-4206 ofU.C.C., Showdyne 509 of Showa Denko K.K., Araldite CY-182 of CIBA-GEIGYA.G Corp., CY-192 and CY-184, Dainippon Ink & Chemicals Inc., EPICLON200 and 400, EPIKOTE 871, 872 of Yuka Shell Epoxy Co., and EP1032H60,ED-5661 and ED-5662 of Celanese Coating Corporation); an aliphaticpolyglycidylether (such as EPIKOTE 190P and 191P of Yuka Shell EpoxyCo., EPOLITE 100MF of Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EPIOL TMPof Nihon Yushi K. K.), and/or the like.

The binder resin may be included in an amount of about 1 wt % to about30 wt %, for example, about 1 wt % to about 20 wt %, based on a totalamount of the solvent based curable composition. When the binder resinis included in these ranges, developability is suitable (e.g.,excellent) and cross-linking is improved to obtain suitable (e.g.,excellent) surface smoothness.

Solvent

The solvent may include, for example, alcohols (such as methanol,ethanol, and/or the like); glycol ethers (such as ethylene glycolmethylether, ethylene glycol ethylether, propylene glycol methylether,and/or the like); cellosolve acetates (such as methyl cellosolveacetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and/orthe like); carbitols (such as methylethyl carbitol, diethyl carbitol,diethylene glycol monomethylether, diethylene glycol monoethylether,diethylene glycol dimethylether, diethylene glycol methylethylether,diethylene glycol diethylether, and/or the like); propylene glycolalkylether acetates (such as propylene glycol monomethylether acetate,propylene glycol propylether acetate, and/or the like); ketones (such asmethylethylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone,methyl-n-propylketone, methyl-n-butylketone, methyl-n-amylketone,2-heptanone, and/or the like); saturated aliphatic monocarboxylic acidalkyl esters (such as ethyl acetate, n-butyl acetate, isobutyl acetate,and/or the like); lactate esters (such as methyl lactate, ethyl lactate,and/or the like); hydroxy acetic acid alkyl esters (such as methylhydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, and/or thelike); acetic acid alkoxyalkyl esters (such as methoxymethyl acetate,methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate,ethoxyethyl acetate, and/or the like); 3-hydroxypropionic acid alkylesters (such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate,and/or the like); 3-alkoxypropionic acid alkyl esters (such as methyl3-methoxypropionate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, methyl 3-ethoxypropionate, and/or the like);2-hydroxypropionic acid alkyl ester (such as methyl 2-hydroxypropionate,ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and/or the like);2-alkoxypropionic acid alkyl esters (such as methyl 2-methoxypropionate,ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl2-ethoxypropionate, and/or the like); 2-hydroxy-2-methylpropionic acidalkyl esters (such as methyl 2-hydroxy-2-methylpropionate, ethyl2-hydroxy-2-methylpropionate, and/or the like);2-alkoxy-2-methylpropionic acid alkyl esters (such as methyl2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and/orthe like); esters (such as 2-hydroxyethyl propionate,2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl2-hydroxy-3-methylbutanoate, and/or the like); and/or ketonate esters(such as ethyl pyruvate, and/or the like), and in addition, may includeN-methylformamide, N,N-dimethyl formamide, N-methylformanilide,N-methylacetamide, N,N-dimethyl acetamide, N-methylpyrrolidone,dimethylsulfoxide, benzylethylether, dihexylether, acetylacetone,isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethylmaleate, γ-butyrolactone, ethylene carbonate, propylene carbonate,phenyl cellosolve acetate, and/or the like, but the present disclosureis not limited thereto.

For example, the solvent may be desirably glycol ethers (such asethylene glycol monoethylether, ethylene diglycolmethylethylether,and/or the like); ethylene glycol alkylether acetates (such as ethylcellosolve acetate, and/or the like); esters (such as 2-hydroxy ethylpropionate, and/or the like); carbitols (such as diethylene glycolmonomethylether, and/or the like); propylene glycol alkylether acetates(such as propylene glycol monomethylether acetate, propylene glycolpropylether acetate, and/or the like); alcohols (such as ethanol, and/orthe like), or a combination thereof.

For example, the solvent may be a polar solvent including propyleneglycol monomethylether acetate, dipropylene glycol methylether acetate,ethanol, ethylene glycoldimethylether, ethylenediglycolmethylethylether,diethylene glycoldimethylether, 2-butoxyethanol, N-methylpyrrolidine,N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone or, acombination thereof.

The solvent may be included in an amount of about 20 wt % to about 80 wt%, for example, about 35 wt % to about 80 wt %, based on a total amountof the solvent based curable composition. When the solvent is withinthese ranges, the solvent based curable composition has appropriateviscosity and thus may have suitable (e.g., excellent) coating propertywhen coated in a large area through spin-coating and/or slit-coating.

In one embodiment, the solvent based curable composition may furtherinclude at least one of a monomer having a carbon-carbon double bond atthe terminal end, a polymerization initiator, a diffusing agent, andother additives.

The monomer having the carbon-carbon double bond may be included in anamount of about 1 wt % to about 10 wt %, for example, about 2 wt % toabout 8 wt %, based on a total amount of the curable composition. Whenthe monomer having the carbon-carbon double bond is included withinthese ranges, curing at exposure during a pattern forming processes issufficiently performed, and heat resistance, light resistance, chemicalresistance, resolution, and close contacting (e.g., adhesion) propertiesof the pattern are improved.

The polymerization initiator may be included in an amount of about 0.1wt % to about 10 wt %, for example, about 0.1 wt % to about 5 wt %,based on a total amount of the solvent based curable composition. Whenthe polymerization initiator is included within these ranges, a balancebetween sensitivity and developability during exposure is improved and apattern having improved resolution without a residual film may beobtained.

The diffusing agent may be included in an amount of about 0.1 wt % toabout 20 wt %, for example, about 1 wt % to about 15 wt %, based on atotal amount of the solvent based curable composition. When thediffusing agent is included in an amount of less than about 1 wt % basedon a total amount of the solvent based curable composition, it isdifficult to expect a photo-conversion efficiency improvement effect dueto the usage of the diffusing agent, while when it is included in anamount of greater than about 20 wt %, pattern characteristics may bedeteriorated.

For example, the solvent based curable composition may be aphotosensitive resin composition. In this case, the solvent basedcurable composition may include a photopolymerization initiator as thepolymerization initiator.

Another embodiment provides a cured layer manufactured utilizing theaforementioned non-solvent curable composition and/or solvent basedcurable composition, a color filter including the cured layer, and adisplay device including the color filter.

One of the methods of manufacturing the cured layer may include coatingthe aforementioned non-solvent curable composition and/or solvent basedcurable composition on a substrate utilizing an ink-jet spraying methodto form a pattern (S1); and curing the pattern (S2).

(S1) Formation of Pattern

The non-solvent curable composition may desirably be coated to be about0.5 μm to about 20 μm in thickness on a substrate in an ink-jet sprayingmethod. The ink-jet spraying method may form a pattern by spraying asingle color per each nozzle and thus repeating the spraying as manytimes as the number of colors needed, but the pattern may be formed byconcurrently or simultaneously spraying the number of colors neededthrough each ink-jet nozzle in order to reduce the number of processes.That is, the pattern may be formed by concurrently spraying the numberof colors needed through a plurality of nozzles (e.g., each containingone of the colors).

(S2) Curing

The obtained pattern is cured to obtain a pixel. Herein, the curingmethod may be thermal curing and/or photocuring process. The thermalcuring process may be performed at greater than or equal to about 100°C., desirably, in a range of about 100° C. to about 300° C., and moredesirably, in a range of about 160° C. to about 250° C. The photocuringprocess may include irradiating an actinic ray such as a UV ray of about190 nm to about 450 nm, for example, about 200 nm to about 500 nm. Theirradiating is performed by utilizing a light source such as a mercurylamp (with a low pressure, a high pressure, or an ultrahigh pressure), ametal halide lamp, an argon gas laser, and/or the like. An X ray, anelectron beam, and/or the like may also be utilized as needed.

The other method of manufacturing the cured layer may includemanufacturing a cured layer utilizing the aforementioned non-solventcurable composition and/or solvent based curable composition by alithographic method as follows.

(1) Coating and Film Formation

The aforementioned curable resin composition is coated to have a desiredthickness, for example, a thickness from about 2 μm to about 10 μm, on asubstrate (which has undergone a set or predetermined pretreatment),utilizing a spin coating method, a slit coating method, a roll coatingmethod, a screen-printing method, an applicator method, and/or the like.Then, the coated substrate is heated at a temperature of about 70° C. toabout 90° C. for 1 minute to 10 minutes to remove a solvent and to forma film.

(2) Exposure

The resultant film is irradiated by an actinic ray such as a UV ray ofabout 190 nm to about 450 nm, for example, about 200 nm to about 500 nm,through a mask with a set or predetermined shape to form a desiredpattern. The irradiation is performed by utilizing a light source suchas a mercury lamp (with a low pressure, a high pressure, or an ultrahighpressure), a metal halide lamp, an argon gas laser, and/or the like. AnX ray, an electron beam, and/or the like may be also utilized as needed.

Exposure process utilizes, for example, a light dose of 500 mJ/cm² orless (with a 365 nm sensor) when a high pressure mercury lamp isutilized. However, the light dose may vary depending on kinds of eachcomponent of the curable composition, their combination ratio, and/or adry film thickness.

(3) Development

After the exposure process, an alkali aqueous solution is utilized todevelop the exposed film by dissolving and removing an unnecessary partexcept the exposed part, thereby forming an image pattern. In otherwords, when the alkali developing solution is utilized for thedevelopment, a non-exposed region is dissolved, and an image colorfilter pattern is formed.

(4) Post-Treatment

The developed image pattern may be heated again or irradiated by anactinic ray and/or the like for curing, in order to accomplish suitable(e.g., excellent) quality in terms of heat resistance, light resistance,close contacting (e.g., adhesion) properties, crack-resistance, chemicalresistance, high strength, storage stability, and/or the like.

Hereinafter, the subject matter of the present disclosure is illustratedin more detail with reference to examples. These examples, however, arenot in any sense to be interpreted as limiting the scope of thedisclosure.

Preparation of Surface-Modified Quantum Dot Dispersion PREPARATIONEXAMPLE 1

92 g of thioglycolic acid (Sigma Aldrich Co., Ltd.), 400 g ofpolyoxyethylene monomethyl ether (Hannong Chemicals Inc.), 20 g ofp-toluenesulfonic acid monohydrate (Sigma Aldrich Co., Ltd.), and 500 mlof cyclohexane were put together, and then, while the mixture was heatedunder a nitrogen atmosphere, so that cyclohexane could be refluxed,water produced therein was removed by utilizing a dean stark apparatus.When water was no longer produced, the reactants were cooled down toroom temperature and then, washed by utilizing ethyl acetate anddistilled water. The organic layer was neutralized by utilizing a NaOHdiluent. Subsequently, the neutralized resultant was washed severaltimes by utilizing distilled water, treated by utilizing MgSO₄ to drythe moisture, and then, concentrated under a reduced pressure to finallyobtain a compound represented by Chemical Formula 1-1.

Preparation of Surface-Modified Quantum Dot Dispersion

A magnetic bar was put in a 3-neck round-bottomed round flask, and aquantum dot-CHA (cyclohexyl acetate) solution (solid content: 26 wt % to27 wt %) was weighed and added thereto. The compound (ligand)represented by Chemical Formula 1-1 prepared above was added thereto.

The mixture was well mixed for 1 minute and then, stirred at 80° C.under a nitrogen atmosphere. When the reaction was complete, theresultant was cooled down to room temperature, and added to cyclohexaneto get precipitates. The precipitated quantum dot powder was separatedfrom the cyclohexane through centrifugation. A clear solution was pouredout and discarded, and then, the precipitates were sufficiently dried ina vacuum oven for one day to obtain surface-modified quantum dots.

The surface-modified quantum dots were stirred (e.g., mixed by stirring)with a monomer represented by Chemical Formula 2-1 (triethylene glycoldimethacrylate, Miwon Commercial Co., Ltd.) for 12 hours to obtainsurface-modified quantum dot dispersion.

PREPARATION EXAMPLE 2

92 g of thioglycolic acid (Sigma Aldrich Co., Ltd.), 206 g oftripropylene glycol monomethyl ether (a mixture of isomers, TCI), 10 gof p-toluenesulfonic acid monohydrate (Sigma Aldrich Co., Ltd.), and 500ml of cyclohexane were put together, and then, while the mixture washeated under a nitrogen atmosphere, so that cyclohexane could berefluxed, water generated therein was removed by utilizing a dean starkapparatus. When water was no longer generated, the reactants were cooleddown to room temperature and then, washed by utilizing ethyl acetate andan excessive amount of distilled water. The organic layer wasneutralized by utilizing a NaOH diluent. Subsequently, the neutralizedresultant was washed several times by utilizing distilled water, treatedby utilizing MgSO₄ to dry moisture, and then, concentrated under areduced pressure to finally obtain a compound represented by ChemicalFormula 1-2.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was prepared according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-2 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 3

106 g of 3-mercaptopropionic acid (Sigma Aldrich Co., Ltd.), 400 g ofpolyoxyethylene monomethyl ether (Hannong Chemicals Inc.), 20 g ofp-toluenesulfonic acid monohydrate (Sigma Aldrich Co., Ltd.), and 500 mlof cyclohexane were put together, and then, while the mixture was heatedunder a nitrogen atmosphere so that cyclohexane could be refluxed, watergenerated therein was removed by utilizing a dean stark apparatus. Whenwater was no longer generated, the reactants were cooled down to roomtemperature and then, washed by utilizing ethyl acetate and distilledwater. The organic layer was neutralized by utilizing a NaOH diluent.Subsequently, the neutralized resultant was washed several times byutilizing distilled water, treated by utilizing MgSO₄ to dry moisture,and then, concentrated under a reduced pressure to finally obtain acompound represented by Chemical Formula 1-3.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-3 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 4

106 g of 3-mercaptopropionic acid (Sigma Aldrich Co., Ltd.), 520 g ofpolyoxyethylene cumyl phenyl ether (Hannong Chemicals Inc.), 26 g ofp-toluenesulfonic acid monohydrate (Sigma Aldrich Co., Ltd.), and 500 mlof cyclohexane were put together, and then, while the mixture was heatedunder a nitrogen atmosphere so that cyclohexane could be refluxed, watergenerated therein was removed by utilizing a dean stark apparatus. Whenwater was no longer produced, the reactants were cooled down to roomtemperature and then, washed by utilizing ethyl acetate and distilledwater. The organic layer was neutralized by utilizing a NaOH diluent.Subsequently, the neutralized resultant was washed several times byutilizing distilled water, treated by utilizing MgSO₄ to dry moisture,and then, concentrated under a reduced pressure to finally obtain acompound represented by Chemical Formula 1-4.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-4 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 5

106 g of 3-mercaptopropionic acid (Sigma Aldrich Co., Ltd.), 934 g ofpolyoxyethylene styrenated phenyl ether (Hannong Chemicals Inc.), 46 gof p-toluenesulfonic acid monohydrate (Sigma Aldrich Co., Ltd.), and1000 ml of cyclohexane were put together, and then, while the mixturewas heated under a nitrogen atmosphere so that cyclohexane could berefluxed, water generated therein was removed by utilizing a dean starkapparatus. When water was no longer produced, the reactants were cooleddown to room temperature and then, washed by utilizing ethyl acetate anddistilled water. The organic layer was neutralized by utilizing a NaOHdiluent. Subsequently, the neutralized resultant was washed severaltimes by utilizing distilled water, treated by utilizing MgSO₄ to drymoisture, and then, concentrated under a reduced pressure to finallyobtain a compound represented by Chemical Formula 1-5.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-5 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 6

191 g of p-toluenesulfonic chloride and 150 mL of a THF diluted solutionwere slowly injected into a mixed solution of 208 g of tetraethyleneglycol monomethyl ether, 44 g of NaOH, 500 mL of THF (tetrahydrofuran),and 100 mL of distilled water at 0° C. After 30 minutes, the injectionis completed, the obtained mixture was continuously stirred at roomtemperature for 12 hours. When a reaction was complete, the resultantwas purified through processes of extraction, neutralization, andconcentration and then, sufficiently dried in a vacuum oven. Theobtained product was put in a flask and dissolved in ethanol under anitrogen atmosphere. 4 equivalents of thiourea were added thereto, andthe obtained mixture was stirred at 100° C. for 12 hours. A NaOH dilutedsolution was injected into the reactants and then, further stirred forabout 5 hours. When a reaction was complete, the resultant was washedseveral times and extracted with distilled water and a hydrochloric aciddiluted solution, neutralized, concentrated and then, sufficiently driedin a vacuum oven to finally obtain a compound represented by ChemicalFormula 1-6.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-6 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 7

191 g of p-toluenesulfonic chloride and 150 mL of a THF diluted solutionwere slowly injected into a mixed solution of 400 g of polyoxyethylenemonomethyl ether (Hannong Chemicals Inc.), 44 g of NaOH, 500 mL of THF,and 100 mL of distilled water at 0° C. After 30 minutes, the injectionis completed, the obtained mixture was continuously stirred at roomtemperature for about 12 hours. When a reaction was complete, theresultant was purified through processes of extraction, neutralization,and concentration and then, sufficiently dried in a vacuum oven. Theobtained product was put in a flask and then, dissolved in ethanol undera nitrogen atmosphere. 4 equivalents of thiourea were added thereto andthen, stirred at 100° C. for 12 hours. A NaOH diluted solution wasinjected into the reactants and then, further stirred for about 5 hours.When a reaction was complete, the resultant was washed several times andextracted by utilizing distilled water and a hydrochloric acid dilutedsolution, neutralized, concentrated, and then, sufficiently dried in avacuum oven to finally obtain a compound represented by Chemical Formula1-7.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-7 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 8

191 g of p-toluenesulfonic chloride and 150 mL of a THF diluted solutionwere slowly injected into a mixed solution of 270 g of polyoxyethylenephenyl ether (Hannong Chemicals Inc.), 44 g of NaOH, 500 mL of THF, and100 mL of distilled water at 0° C. After 30 minutes, the injection iscompleted, the obtained mixture was continuously stirred at roomtemperature for 12 hours. When a reaction was complete, the resultantwas purified through processes of extraction, neutralization, andconcentration and then, dried in a vacuum oven. The obtained product wasput in a flask and then, dissolved in ethanol under a nitrogenatmosphere. 4 equivalents of thiourea was added thereto and then,stirred at 100° C. for 12 hours. A NaOH diluted solution was injectedinto the reactants and then, further stirred for about 5 hours. When areaction was complete, the resultant was washed several times andextracted with distilled water and a hydrochloric acid diluted solution,neutralized, concentrated, and then, sufficiently dried in a vacuum ovento finally obtain a compound represented by Chemical Formula 1-8.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-8 was utilized instead of the ligand representedby Chemical Formula 1-1.

PREPARATION EXAMPLE 9

191 g of p-toluenesulfonic chloride and 150 mL of a THF diluted solutionwere slowly injected into a mixed solution of 270 g of polyoxyethylenephenyl ether (Hannong Chemicals Inc.), 44 g of NaOH, 500 mL of THF, and100 mL of distilled water at 0° C. After 30 minutes, the injection iscompleted, the obtained mixture was continuously stirred at roomtemperature for 12 hours. When the reaction was complete, the resultantwas purified through extraction, neutralization, and concentration andthen, sufficiently dried in a vacuum oven. The obtained product was putin a flask and then, dissolved in ethanol under a nitrogen atmosphere. 4equivalents of thiourea were added thereto and then, stirred at 100° C.for 12 hours. A NaOH diluted solution was injected into the reactantsand then, further stirred for about 5 hours. When a reaction wascomplete, the resultant was washed several times and extracted withwater and a hydrochloric acid diluted solution, concentrated, and then,sufficiently dried in a vacuum oven to finally obtain a compoundrepresented by Chemical Formula 1-9.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula 1-9 was utilized instead of the ligand representedby Chemical Formula 1-1.

COMPARATIVE PREPARATION EXAMPLE 1

92 g of thioglycolic acid (Sigma Aldrich Co., Ltd.), 164 g oftriethylene monomethyl ether (TCI), 8 g of p-toluenesulfonic acidmonohydrate (Sigma Aldrich Co., Ltd.), and 500 ml of cyclohexane wereput together, and then, while the mixture was heated under a nitrogenatmosphere, so that cyclohexane could be refluxed, water generatedtherefrom was removed by utilizing a dean stark apparatus. When waterwas no longer produced, the reactants were cooled down to roomtemperature and then, washed by utilizing ethyl acetate and distilledwater. The organic layer was neutralized by utilizing a NaOH diluent.Subsequently, the neutralized resultant was washed several times byutilizing distilled water, treated by utilizing MgSO₄ to dry moisture,and then, concentrated under a reduced pressure to finally obtain acompound represented by Chemical Formula C.

Preparation of Surface-Modified Quantum Dot Dispersion

Surface-modified quantum dot dispersion was obtained according to thesame method as Preparation Example 1 except that the ligand representedby Chemical Formula C was utilized instead of the ligand represented byChemical Formula 1-1.

Evaluation 1: Dispersion

The quantum dot dispersions of Preparation Examples 1 to 9 andComparative Preparation Example 1 were each respectively measured threetimes with respect to particle sizes by utilizing a microparticle sizeanalyzer and averaged, and the results are shown in Table 1.

TABLE 1 Particle size (D50) (nm) Preparation Example 1 14.4 PreparationExample 2 14.5 Preparation Example 3 13.4 Preparation Example 4 13.3Preparation Example 5 13.6 Preparation Example 6 14.0 PreparationExample 7 14.1 Preparation Example 8 14.1 Preparation Example 9 14.0Comparative Preparation Example 1 15.0

Referring to Table 1, each of the quantum dot dispersion according toPreparation Examples 1 to 9 exhibited a narrow particle sizedistribution, which shows that the quantum dots were well dispersed in ahigh boiling-point and high surface-tension solvent (e.g., monomer), butthe quantum dot dispersion according to Comparative Preparation Example1 exhibited a wide particle size distribution, which shows that thequantum dots were not well dispersed in the high boiling-point and highsurface-tension solvent (e.g., monomer).

Preparation of Non-Solvent Curable Composition EXAMPLE 1

The dispersion according to Preparation Example 1 was weighed and then,mixed and diluted with the monomer represented by Chemical Formula 2-1,and a polymerization inhibitor (methylhydroquinone, Tokyo ChemicalIndustry Co., Ltd.) was added thereto and then, stirred for 5 minutes.Subsequently, a photoinitiator (TPO-L, Polynetron) was injectedthereinto, and a light diffusing agent (TiO₂; SDT89, Iridos Co., Ltd.)was added thereto. The entire dispersion was stirred for 1 hour toprepare a non-solvent curable composition. 40 wt % of the quantum dots,48 wt % of the monomer represented by Chemical Formula 2-1, 1 wt % ofthe polymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt %of the light diffusing agent were included based on a total amount ofthe non-solvent curable composition.

EXAMPLE 2

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 2 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 3

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 3 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 4

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 4 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 5

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 5 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 6

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 6 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 7

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 7 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 8

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 8 was utilized instead of the dispersion according toPreparation Example 1.

EXAMPLE 9

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to PreparationExample 9 was utilized instead of the dispersion according toPreparation Example 1.

COMPARATIVE EXAMPLE 1

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that the dispersion according to ComparativePreparation Example 1 was utilized instead of the dispersion accordingto Preparation Example 1.

COMPARATIVE EXAMPLE 2

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that 50 wt % of the quantum dots, 38 wt % ofthe monomer represented by Chemical Formula 2-1, 1 wt % of thepolymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % ofthe light diffusing agent were utilized based on a total amount of thenon-solvent curable composition.

COMPARATIVE EXAMPLE 3

A non-solvent curable composition was prepared according to the samemethod as Example 1 except that 6 wt % of the quantum dots, 82 wt % ofthe monomer represented by Chemical Formula 2-1, 1 wt % of thepolymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % ofthe light diffusing agent were utilized based on a total amount of thenon-solvent curable composition.

Evaluation 2: Evaluation of Optical Characteristics

Each composition according to Examples 1 to 9 and Comparative Examples 1to 3 was coated to be about 15 μm thick on glass substrates and yellowphotoresists (YPR) respectively with a spin coater (800 rpm, 5 seconds,Opticoat MS-A150, Mikasa Co., Ltd.) and exposed with 5000 mJ (83° C., 10seconds) with a 395 nm UV exposer under a nitrogen atmosphere to preparea cured film. Subsequently, a 2 cm×2 cm single film specimen of eachcured film was loaded in an integrating sphere equipment (QE-2100,Otsuka Electronics, Co., Ltd.) and measured with respect to a lightabsorption rate and light efficiency, and the results are shown in Table2.

TABLE 2 External Maximum Light quantum emission absorption efficiencywavelength rate (%) (E.Q.E) (%) (nm) Example 1 glass 94.7 28.5 541 YPR100 25.3 542 Example 2 glass 95 29 542 YPR 100 26.8 542 Example 3 glass94.3 30.5 542 YPR 100 26.8 542 Example 4 glass 96 28.6 543 YPR 100 25.6543 Example 5 glass 94.3 29.1 542 YPR 100 24.7 542 Example 6 glass 94.832 541 YPR 100 28.7 541 Example 7 glass 96.8 28.8 543 YPR 100 28.2 543Example 8 glass 92.8 33.8 535 YPR 100 28.3 534 Example 9 glass 93.8 33.8535 YPR 100 29.4 542 Comparative Example 1 glass 95.3 25.1 542 YPR 10022.8 542 Comparative Example 2 glass 98.1 29.1 544 YPR 100 24.4 544Comparative Example 3 glass 52.1 14.1 525 YPR 96 10 525

Referring to Table 2, the non-solvent curable composition according toan embodiment exhibited suitable (e.g., very excellent) opticalcharacteristics.

Preparation of Solvent Based Curable Composition EXAMPLE 10

The dispersion according to Preparation Example 5 was weighed todisperse quantum dots (23 wt %) in dimethyl adipate (45 wt %) and mixedwith a cardo-based binder resin (TSR-TA01, TAKOMA) (8 wt %) to prepare aquantum dot dispersion. Subsequently, OXT-221 (Toagosei Co., Ltd.) (1 wt%) and PFM-02 (SMS) (16.5 wt %) as a thermosetting monomer, a lightdiffusing agent (TiO₂; SDT89, Iridos Co., Ltd.) (2 wt %), glycoldi-3-mercaptopropionate (Bruno Bock Chemische Fabrik GMBH & CO., KG)(4.2 wt %), and methyl hydroquinone (TCI) (0.3 wt %) as a polymerizationinhibitor were mixed, and the quantum dot dispersion was added theretoand then, stirred to prepare a solvent based curable composition.

EXAMPLE 11

Each solvent based curable composition (photosensitive resincomposition) was prepared utilizing the following components in acorresponding amount.

Specifically, a photopolymerization initiator is dissolved in a solvent,and the solution is sufficiently stirred at room temperature for 2hours. Subsequently, a binder resin along with quantum dots and adispersing agent (TEGO D685 made by EVONIK) are added thereto, and theobtained mixture is stirred again at room temperature for 2 hours. Then,a diffusing agent and a fluorine-based surfactant were added thereto andthen, stirred for 1 hour at room temperature, and a product therein wasfiltered three times to remove impurities and prepare a photosensitiveresin composition.

1) Quantum dot: 12 wt % of quantum dots obtained from PreparationExample 1

2) Binder resin: 25 wt % of a cardo-based binder resin (TSR-TA01,TAKOMA)

3) Polymerizable monomer: 5.4 wt % of pentaerythritolhexamethacrylate(DPHA, Nippon Kayaku Co. Ltd.)

4) Photopolymerization initiator: 0.7 wt % ofdiphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, Sigma-AldrichCorporation)

5) Solvent: 39 wt % of dimethyladipate

6) Diffusing agent: 39 wt % of titanium dioxide dispersion (a TiO₂ solidcontent: 20 wt %, an average particle diameter: 200 nm, DittoTechnology)

7) Thiol additive: 2 wt % of glycol di-3-mercaptopropionate (BRUNO BOCK)

8) Other additives: 0.9 wt % of a fluorine-based surfactant (F-554, DICCo., Ltd.)

Evaluation 3: Photo-Conversion Rate and Photo-Conversion MaintenanceRate of Quantum Dots

The curable compositions according to Examples 10 and 11 wererespectively coated to be 6 μm thick on a glass substrate with a spincoater (150 rpm, Opticoat MS-A150, Mikasa Co., Ltd.) and then, dried ona hot-plate at 80° C. for 1 minute to obtain a single film, and aninitial blue photo-conversion rate thereof was measured (First Step).

The obtained film was dried in a forced convection dryer at 180° C. for30 minutes, and a blue photo-conversion rate thereof was measured(Second Step).

In the first and second steps, a photo-conversion rate and aphoto-conversion maintenance rate of incident blue light from BLU(Backlight Unit) into green were evaluated, and the results are shown inTable 3. Herein, a blue photo-conversion rate (Green/Blue) was measuredby utilizing a CAS 140 CT spectrometer and specifically, through putting(e.g., loading) a bare glass on blue BLU (455 nm) covered with adiffusing film to first obtain a reference with a detector, putting(e.g., loading) each single film coated with the solvent based curablecompositions according to Examples 10 and 11, and calculating a peakincrease converted into green light relative to an absorption peakdecrease of blue light. That is, the photo-conversion rate is calculateas the ratio of the amount of increase in the peak height of the greenlight to the amount of decrease in the peak height of the blue light inthe absorption spectrum, each based on the bare glass on blue BLU (455nm) covered with the diffusing film. In addition, how much thephoto-conversion rate in the first step was maintained in the secondstep, that is, a photo-conversion maintenance rate from the first stepto the second step was also measured, and the results are shown in Table3.

In addition, as for the solvent based curable composition of Example 11,a photo-conversion rate was measured with an exposer (ghi broadband,Ushio Inc.) by performing post-baking (POB) in a convection clean oven(Jongro) at 180° C. for 30 minutes after irradiating UV with a power of100 mJ/cm², and the results are shown in Table 4.

TABLE 3 (unit: %) Example 10 Example 11 Photo-conversion rate 29 26Photo-conversion maintenance rate 96 94

TABLE 4 (unit: %) Example 11 Initial photo-conversion rate 26Phot-conversion rate after POB is once performed at 22.8 180° C. for 30min

As shown in Tables 3 and 4, the solvent based curable compositionprepared by utilizing surface-modified quantum dots according to anembodiment exhibited smaller deterioration of a blue photo-conversionrate due to a color filter process but exhibited a high photo-conversionmaintenance rate.

Expressions such as “at least one of” or “at least one selected from”when preceding a list of elements, modify the entire list of elementsand do not modify the individual elements of the list. Further, the useof “may” when describing embodiments of the present invention refers to“one or more embodiments of the present invention.” Also, the term“exemplary” is intended to refer to an example or illustration. As usedherein, the term “substantially,” “about,” and similar terms are used asterms of approximation and not as terms of degree, and are intended toaccount for the inherent deviations in measured or calculated valuesthat would be recognized by those of ordinary skill in the art.Moreover, any numerical range recited herein is intended to include allsub-ranges of the same numerical precision subsumed within the recitedrange. For example, a range of “1.0 to 10.0” is intended to include allsubranges between (and including) the recited minimum value of 1.0 andthe recited maximum value of 10.0, that is, having a minimum value equalto or greater than 1.0 and a maximum value equal to or less than 10.0,such as, for example, 2.4 to 7.6. Any maximum numerical limitationrecited herein is intended to include all lower numerical limitationssubsumed therein and any minimum numerical limitation recited in thisspecification is intended to include all higher numerical limitationssubsumed therein. Accordingly, Applicant reserves the right to amendthis specification, including the claims, to expressly recite anysub-range subsumed within the ranges expressly recited herein. All suchranges are intended to be inherently described in this specificationsuch that amending to expressly recite any such subranges would complywith the requirements of 35 U.S.C. § 112, first paragraph, or 35 U.S.C.§ 112(a), and 35 U.S.C. § 132(a).

The terminology used herein is for the purpose of describing particularexample embodiments only and is not intended to be limiting of theinvention. As used herein, the singular forms “a,” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises” and/or “comprising,” when used in this specification,specify the presence of stated features, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,elements, components, and/or groups thereof.

While this disclosure has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the subject matter of the present disclosure is notlimited to the disclosed embodiments, but, on the contrary, is intendedto cover various modifications and equivalent arrangements includedwithin the spirit and scope of the appended claims, and equivalentsthereof. Therefore, the aforementioned embodiments should be understoodto be exemplary but not limiting the subject matter of the presentdisclosure in any way.

What is claimed is:
 1. A quantum dot surface-modified with a compoundrepresented by Chemical Formula 1:

wherein, in Chemical Formula 1, R¹ is a substituted or unsubstituted C1to C10 alkyl group or a substituted or unsubstituted C6 to C20 arylgroup, L¹ to L³ are each independently a substituted or unsubstituted C1to C10 alkylene group, an ester group, or an ether group, and n is aninteger of 3 to 20, provided that when L² is an ester group and L³ is anunsubstituted C1 to C10 alkylene group, n is an integer of 4 to
 20. 2.The quantum dot of claim 1, wherein L¹ and L³ are each independently asubstituted or unsubstituted C1 to C10 alkylene group, and L² is anester group or an ether group.
 3. The quantum dot of claim 1, whereinthe compound represented by Chemical Formula 1 comprises at least oneselected from compounds represented by Chemical Formula 1-1 to ChemicalFormula 1-9:


4. The quantum dot of claim 1, wherein the quantum dot has a maximumfluorescence emission wavelength at about 500 nm to about 680 nm.
 5. Anon-solvent curable composition comprising the quantum dot of claim 1, apolymerizable monomer having a carbon-carbon double bond at a terminalend, and a light diffusing agent, wherein the polymerizable monomer isabout 35 wt % to about 80 wt % in amount based on a total weight of thenon-solvent curable composition, and the non-solvent curable compositiondoes not contain any solvent.
 6. The non-solvent curable composition ofclaim 5, wherein the polymerizable monomer has a molecular weight ofabout 220 g/mol to about 1,000 g/mol.
 7. The non-solvent curablecomposition of claim 5, wherein the polymerizable monomer is representedby Chemical Formula 2: Chemical Formula 2

wherein, in Chemical Formula 2, R² and R³ are each independently ahydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,L⁴ and L⁶ are each independently a substituted or unsubstituted C1 toC10 alkylene group, and L⁵ is a substituted or unsubstituted C1 to C10alkylene group or an ether group.
 8. The non-solvent curable compositionof claim 5, wherein the quantum dot is about 1 wt % to about 60 wt % inamount based on the total weight of the non-solvent curable composition.9. The non-solvent curable composition of claim 5, wherein the lightdiffusing agent comprises barium sulfate, calcium carbonate, titaniumdioxide, zirconia, or a combination thereof.
 10. The non-solvent curablecomposition of claim 5, wherein the non-solvent curable compositionfurther comprises a polymerization initiator.
 11. The non-solventcurable composition of claim 5, wherein the non-solvent curablecomposition further comprises a polymerization inhibitor; malonic acid;3-amino-1,2-propanediol; a silane-based coupling agent; a levelingagent; a fluorine-based surfactant; or a combination thereof.
 12. Asolvent based curable composition comprising the quantum dot of claim 1;a binder resin; and a solvent.
 13. The solvent based curable compositionof claim 12, further comprising a polymerizable monomer, apolymerization initiator, a light diffusing agent, or a combinationthereof.
 14. The solvent based curable composition of claim 12, whereinthe solvent based curable composition is a photosensitive resincomposition.
 15. A curing layer manufactured utilizing the compositionof claim
 5. 16. A curing layer manufactured utilizing the composition ofclaim
 12. 17. A color filter comprising the cured layer of claim
 15. 18.A color filter comprising the cured layer of claim
 16. 19. A displaydevice comprising the color filter of claim
 17. 20. A display devicecomprising the color filter of claim 18.